CN105932323A - Preparation methods of nickel-cobalt-aluminum hydroxide precursor and nickel-cobalt-aluminum ternary lithium-ion positive electrode material - Google Patents
Preparation methods of nickel-cobalt-aluminum hydroxide precursor and nickel-cobalt-aluminum ternary lithium-ion positive electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a preparation method of a hollow urchin-like nickel-cobalt-aluminum composite hydroxide precursor. With a nickel salt, a cobalt salt and an aluminum salt as raw materials, mixed hydrothermal reaction is firstly carried out on the nickel salt and the cobalt salt during preparation and then the aluminum salt is added for hydrothermal reaction; and molar ratio of Ni to Co to Al is (0.6-0.9) to (0.05-0.3) to (0.01-0.1). The invention further provides a preparation method of a nickel-cobalt-aluminum ternary lithium-ion positive electrode material. The hollow urchin-like nickel-cobalt-aluminum composite hydroxide precursor is prepared by the method; the precursor and the lithium salt are mixed and ground by ethyl alcohol and then dried; and the mixture is calcined in an oxygen atmosphere and is cooled to obtain a lithium nickel cobalt aluminum oxide ternary positive electrode material. The hollow urchin-like precursor is obtained; the performance of the nickel-cobalt-aluminum ternary lithium-ion positive electrode material obtained by calcining the hollow urchin-like precursor is also improved; and compared with a traditional solid spherical material, the hollow spherical nickel-cobalt-aluminum positive electrode material has the advantages that the tap density is lower, but the stability performance and the capacity are improved.
Description
Technical field
The present invention relates to belong to energy storage material and electrochemical field, a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide forerunner
Body and the preparation method of nickel cobalt aluminum ternary lithium ion anode material.
Background technology
Positive electrode is the key factor of restriction capacity of lithium ion battery, nickelic system tertiary cathode material have specific discharge capacity high,
The advantage such as low temperature, good rate capability obtains the third generation battery of the attention in market, especially Panasonic and uses on the basis of front two generations
Nickel cobalt lithium aluminate, as positive electrode, all increases in terms of battery capacity, mass energy density, volume energy density, special
This draw electric automobile Model S be exactly use nickel cobalt aluminum ternary material be the lithium ion battery of positive pole.
The nickel cobalt aluminum ternary lithium ion anode material pattern of research preparation at present mostly is medicine ball.
Summary of the invention
The goal of the invention of the present invention is for above-mentioned situation, it is provided that a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma
Preparation method and the preparation method of nickel cobalt aluminum ternary lithium ion anode material.
For achieving the above object, technical solution of the present invention is as follows:
A kind of preparation method of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, with nickel salt, cobalt salt and aluminium salt as raw material,
Prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, first carry out nickel salt and cobalt salt during preparation mixing hydro-thermal
Reaction, adds aluminium salt and carries out hydro-thermal reaction, and Ni:Co:Al mol ratio is (0.6～0.9): (0.05～0.3): (0.01～0.1).
After nickel salt, cobalt salt and carbamide mixing hydro-thermal, obtain hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, described forerunner
The pattern of body is to be covered with the acicular texture that Liao Cong center outwards radiates outside hollow ball, the most hollow Hemicentrotus seu Strongylocentrotus shape, add after aluminium salt along with
The pattern increasing presoma of hydrothermal temperature becomes and is covered with the laminated structure that Liao Cong center outwards radiates outside hollow ball, becomes the most again
Make the return trip empty and be covered with the acicular texture that Liao Cong center outwards radiates outside bulbus cordis.
The present invention also provides for the preparation method of a kind of nickel cobalt aluminum ternary lithium ion anode material, comprises the steps:
(1) said method is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；
(3) calcine under the atmosphere of oxygen, after cooling, obtain lithium nickel cobalt aluminum oxide ternary anode material.
It is preferred that, in described step (2), nickel cobalt aluminum complex hydroxide presoma is with lithium salts in molar ratio
The ratio mixing of nLi:(nNi+nCo+nAl)=1.0-1.1.
It is preferred that, described lithium nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x
≤ 0.9,0.05≤y≤0.3.
It is preferred that, nickel salt and cobalt salt are first mixed hydro-thermal 4～8h by described step (1), add aluminium salt hydro-thermal 8h-20h,
Hydrothermal temperature is 130～220 DEG C.
It is preferred that, with the pH value of carbamide regulation reaction solution in described step (1), Ni, Co, Al tri-element
The mol ratio of mole total amount and carbamide is 1:2.
It is preferred that, in described step (2) lithium salts be lithium sulfate, lithium nitrate, lithium chloride, lithium acetate, the one of lithium oxalate
Kind.
It is preferred that, in described step (3), the atmosphere of calcining is oxygen, and the temperature of calcining is 500～850 DEG C, calcining
Time is 4～10h.
It is preferred that, the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tubular type by described step (3)
With the ramp of 8～10 DEG C/min in stove, in the atmosphere of oxygen, oxidizing roasting obtains lithium nickel cobalt aluminum oxide ternary anode material.
It is preferred that, described nickel salt, cobalt salt and aluminium salt is respectively the sulfate of correspondence, nitrate, chlorate, acetic acid
Salt and oxalates one therein.
The class that nickel cobalt aluminum ternary lithium ion anode material pattern prepared by the present invention is hollow is spherical, as shown in Figure 8.
The present invention compared with prior art has the benefit that
(1) comparing with the mode that nickel salt, cobalt salt, aluminium salt are simultaneously introduced hydro-thermal, nickel salt and cobalt salt are first mixed by the present invention
Hydro-thermal reaction, adding aluminium salt and carry out hydro-thermal reaction, such mode has obtained the presoma of special appearance: hollow Hemicentrotus seu Strongylocentrotus shape
Nickel cobalt aluminum complex hydroxide presoma, and the performance thus calcining the nickel cobalt aluminum ternary lithium ion anode material obtained changed
Kind, it is relatively low that the nickel cobalt aluminum positive electrode of this hollow ball-shape compares tap density with the material of the solid spherical of tradition preparation, but surely
Qualitative energy and capacity all increase；
(2) present invention controls the pH value of reaction solution, and NH by controlling the content of carbamide4 +The surface being attached to crystal presses down
The growth in combinations face and obtain hollow ball, this is to regulate and control reaction solution pH value with alkali in prior art not accomplished.
Accompanying drawing explanation
Fig. 1 is nickel salt and the cobalt salt mixing hydro-thermal SEM of 4 hours figure；
Fig. 2 is the SEM figure of embodiment 1 nickel cobalt aluminum presoma；
Fig. 3 is the SEM figure of embodiment 2 nickel cobalt aluminum presoma；
Fig. 4 is the SEM figure of embodiment 3 nickel cobalt aluminum presoma；
Fig. 5 is the SEM figure of embodiment 4 nickel cobalt aluminum presoma；
Fig. 6 is the XRD figure of embodiment 2 nickel cobalt aluminum tertiary cathode material.
Fig. 7 is the cycle performance figure of embodiment 1 nickel cobalt aluminum tertiary cathode material.
Fig. 8 is the SEM figure of embodiment 1 nickel cobalt aluminum tertiary cathode material finished product.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by disclosed by this specification
Content understand other advantages and effect of the present invention easily.The present invention can also be added by the most different detailed description of the invention
To implement or application, the every details in this specification can also be based on different viewpoints and application, in the essence without departing from the present invention
Various modification or change is carried out under god.
Embodiment 1
The preparation method of a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, comprises the following steps: with nickel nitrate, nitre
Acid cobalt and aluminum nitrate are raw material, prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, Ni:Co:Al mole
Ratio is 0.7:0.25:0.05；First carry out nickel salt and cobalt salt during preparation mixing hydro-thermal 4h, add aluminium salt hydro-thermal 8h, hydro-thermal temperature
Degree is 160 DEG C.With carbamide regulation reaction solution pH value, Ni, Co, Al tri-element mole total amount and the mol ratio of carbamide
It is 1:2.
Fig. 1 is nickel salt and the cobalt salt mixing hydro-thermal SEM of 4 hours figure；
Fig. 2 is the SEM figure of embodiment 1 nickel cobalt aluminum presoma；As in figure 2 it is shown, after nickel salt, cobalt salt and carbamide mixing hydro-thermal,
Obtaining hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, the pattern of described presoma is to be covered with Liao Cong center outside hollow ball
To extraradial acicular texture, the most hollow Hemicentrotus seu Strongylocentrotus shape, after adding aluminium salt, become empty along with the pattern increasing presoma of hydrothermal temperature
It is covered with the laminated structure that Liao Cong center outwards radiates outside bulbus cordis, becomes again the most again and be covered with Liao Cong center outside hollow ball and outwards radiate
Acicular texture；
The preparation method of a kind of nickel cobalt aluminum ternary lithium ion anode material, comprises the steps:
(1) said method is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；Institute's nickel cobalt aluminum complex hydroxide presoma is massaged with lithium salts
You are than nLi:(nNi+nCo+nAl) the ratio mixing of=1.0:1, lithium salts is lithium nitrate；
(3) calcine under the atmosphere of oxygen, the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tube furnace
With the ramp of 8 DEG C/min, the temperature of calcining is 500 DEG C, and the time of calcining is 4h.Lithium nickel cobalt alumina three is obtained after cooling
Unit's positive electrode.Described lithium nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x≤0.9,
0.05≤y≤0.3。
Fig. 8 is the SEM figure of embodiment 1 nickel cobalt aluminum tertiary cathode material finished product, and obtain as can be seen from Fig. can be seen that nickel cobalt
Aluminum tertiary cathode material finished product is hollow ball.
Fig. 7 is the cycle performance figure of embodiment 1 nickel cobalt aluminum tertiary cathode material.
As shown in Figure 7, the nickel cobalt aluminum tertiary cathode material of this hollow ball under 0.1C multiplying power first discharge capacity be
144mAhg-1, after the constant current charge-discharge of 50 circles, its specific volume is maintained at the 92.4% of initial capacity, service life cycle
Excellent.
Embodiment 2
The preparation method of a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, comprises the following steps: with nickel sulfate, sulfur
Acid cobalt and aluminum sulfate are raw material, prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, Ni:Co:Al mole
Ratio is 0.9:0.05:0.05.First nickel salt and cobalt salt are carried out mixing water thermal response during preparation, add aluminium salt and carry out hydro-thermal reaction；
First nickel salt and cobalt salt being mixed hydro-thermal 8h, add aluminium salt hydro-thermal 20h, hydrothermal temperature is 130 DEG C.Molten with carbamide regulation reaction
The pH value of liquid, Ni, Co, Al tri-element mole total amount and the mol ratio of carbamide be 1:2；
Fig. 3 is the SEM figure of embodiment 2 nickel cobalt aluminum presoma；As it is shown on figure 3, after nickel salt, cobalt salt and carbamide mixing hydro-thermal,
Obtaining hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, the pattern of described presoma is to be covered with Liao Cong center outside hollow ball
To extraradial acicular texture, the most hollow Hemicentrotus seu Strongylocentrotus shape, after adding aluminium salt, become empty along with the pattern increasing presoma of hydrothermal temperature
It is covered with the laminated structure that Liao Cong center outwards radiates outside bulbus cordis, becomes again the most again and be covered with Liao Cong center outside hollow ball and outwards radiate
Acicular texture；
The preparation method of a kind of nickel cobalt aluminum ternary lithium ion anode material, comprises the steps:
(1) said method is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；Institute's nickel cobalt aluminum complex hydroxide presoma is massaged with lithium salts
You are than nLi:(nNi+nCo+nAl) the ratio mixing of=1.0-1.1.Lithium salts is lithium sulfate；
(3) calcine under the atmosphere of oxygen, the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tube furnace
With the ramp of 10 DEG C/min, the temperature of calcining is 850 DEG C, and the time of calcining is 10h.Lithium nickel cobalt alumina is obtained after cooling
Tertiary cathode material.Described lithium nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x≤0.9,
0.05≤y≤0.3。
Fig. 6 is the XRD figure of embodiment 2 nickel cobalt aluminum tertiary cathode material.The nickel cobalt aluminum tertiary cathode material finished product obtained is hollow
Ball.
Embodiment 3
The preparation method of a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, comprises the following steps: with Nickel dichloride., chlorine
Changing cobalt and aluminum chloride is raw material, prepares hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, described nickel salt,
Cobalt salt and aluminium salt are respectively corresponding sulfate, nitrate, chlorate, acetate and oxalates one therein.Ni:Co:Al
Mol ratio is 0.6:0.3:0.1.First nickel salt and cobalt salt are carried out mixing water thermal response during preparation, add aluminium salt and carry out hydro-thermal reaction；
First nickel salt and cobalt salt being mixed hydro-thermal 6h, add aluminium salt hydro-thermal 16h, hydrothermal temperature is 180 DEG C.Molten with carbamide regulation reaction
The pH value of liquid, Ni, Co, Al tri-element mole total amount and the mol ratio of carbamide be 1:2.
Fig. 4 is the SEM figure of embodiment 3 nickel cobalt aluminum presoma；As shown in Figure 4, after nickel salt, cobalt salt and carbamide mixing hydro-thermal,
Obtaining hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, the pattern of described presoma is to be covered with Liao Cong center outside hollow ball
To extraradial acicular texture, the most hollow Hemicentrotus seu Strongylocentrotus shape, after adding aluminium salt, become empty along with the pattern increasing presoma of hydrothermal temperature
It is covered with the laminated structure that Liao Cong center outwards radiates outside bulbus cordis, becomes again the most again and be covered with Liao Cong center outside hollow ball and outwards radiate
Acicular texture.
The preparation method of a kind of nickel cobalt aluminum ternary lithium ion anode material, comprises the steps:
(1) said method is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；Institute's nickel cobalt aluminum complex hydroxide presoma is massaged with lithium salts
You are than nLi:(nNi+nCo+nAl) the ratio mixing of=1.0-1.1.Lithium salts is lithium chloride.
(3) calcine under the atmosphere of oxygen, the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tube furnace
With the ramp of 9 DEG C/min, the temperature of calcining is 700 DEG C, and the time of calcining is 6h.Lithium nickel cobalt alumina three is obtained after cooling
Unit's positive electrode.Described lithium nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x≤0.9,
0.05≤y≤0.3.The nickel cobalt aluminum tertiary cathode material finished product obtained is hollow ball.
Embodiment 4
The preparation method of a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, comprises the following steps: with nickel acetate, vinegar
Acid cobalt and aluminum acetate are raw material, prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, Ni:Co:Al mole
Ratio is 0.75:0.15:0.01.First nickel salt and cobalt salt are carried out mixing water thermal response during preparation, add aluminium salt and carry out hydro-thermal reaction；
First nickel salt and cobalt salt being mixed hydro-thermal 5h, add aluminium salt hydro-thermal 14h, hydrothermal temperature is 160 DEG C.Molten with carbamide regulation reaction
The pH value of liquid, Ni, Co, Al tri-element mole total amount and the mol ratio of carbamide be 1:2.
Fig. 5 is the SEM figure of embodiment 4 nickel cobalt aluminum presoma；As it is shown in figure 5, after nickel salt, cobalt salt and carbamide mixing hydro-thermal,
Obtaining hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, the pattern of described presoma is to be covered with Liao Cong center outside hollow ball
To extraradial acicular texture, the most hollow Hemicentrotus seu Strongylocentrotus shape, after adding aluminium salt, become empty along with the pattern increasing presoma of hydrothermal temperature
It is covered with the laminated structure that Liao Cong center outwards radiates outside bulbus cordis, becomes again the most again and be covered with Liao Cong center outside hollow ball and outwards radiate
Acicular texture.
The preparation method of a kind of nickel cobalt aluminum ternary lithium ion anode material, comprises the steps:
(1) said method is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；Institute's nickel cobalt aluminum complex hydroxide presoma is massaged with lithium salts
You are than nLi:(nNi+nCo+nAl) the ratio mixing of=1.0-1.1.Lithium salts is lithium acetate.
(3) calcine under the atmosphere of oxygen, the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tube furnace
With the ramp of 9 DEG C/min, the temperature of calcining is 800 DEG C, and the time of calcining is 8h.Lithium nickel cobalt alumina three is obtained after cooling
Unit's positive electrode.Described lithium nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x≤0.9,
0.05≤y≤0.3.The nickel cobalt aluminum tertiary cathode material finished product obtained is hollow ball.
Embodiment 5
The preparation method of a kind of hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, comprises the following steps: with nickel oxalate, grass
Acid cobalt and oxalic acid aluminum are raw material, prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, Ni:Co:Al mole
Ratio is 0.85:0.05:0.1.First nickel salt and cobalt salt are carried out mixing water thermal response during preparation, add aluminium salt and carry out hydro-thermal reaction；
First nickel salt and cobalt salt being mixed hydro-thermal 5h, add aluminium salt hydro-thermal 10h, hydrothermal temperature is 220 DEG C.Molten with carbamide regulation reaction
The pH value of liquid, Ni, Co, Al tri-element mole total amount and the mol ratio of carbamide be 1:2.
After nickel salt, cobalt salt and carbamide mixing hydro-thermal, obtain hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, described forerunner
The pattern of body is to be covered with the acicular texture that Liao Cong center outwards radiates outside hollow ball, the most hollow Hemicentrotus seu Strongylocentrotus shape, add after aluminium salt along with
The pattern increasing presoma of hydrothermal temperature becomes and is covered with the laminated structure that Liao Cong center outwards radiates outside hollow ball, becomes the most again
Make the return trip empty and be covered with the acicular texture that Liao Cong center outwards radiates outside bulbus cordis.
The preparation method of a kind of nickel cobalt aluminum ternary lithium ion anode material, comprises the steps:
(1) said method is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；Institute's nickel cobalt aluminum complex hydroxide presoma is massaged with lithium salts
You are than nLi:(nNi+nCo+nAl) the ratio mixing of=1.0-1.1.Lithium salts is lithium oxalate.
(3) calcine under the atmosphere of oxygen, the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tube furnace
With the ramp of 10 DEG C/min, the temperature of calcining is 800 DEG C, and the time of calcining is 9h.Lithium nickel cobalt alumina three is obtained after cooling
Unit's positive electrode.Described lithium nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x≤0.9,
0.05≤y≤0.3.The nickel cobalt aluminum tertiary cathode material finished product obtained is hollow ball.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this skill
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of art.Therefore, all institutes
Belong to and technical field has all equivalences that usually intellectual is completed under without departing from disclosed spirit and technological thought
Modify or change, must be contained by the claim of the present invention.
Claims (10)
1. the preparation method of a hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma, it is characterised in that: with nickel salt, cobalt
Salt and aluminium salt are raw material, prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma by hydro-thermal method, during preparation first by nickel salt and
Cobalt salt carries out mixing water thermal response, adds aluminium salt and carries out hydro-thermal reaction, and Ni:Co:Al mol ratio is (0.6～0.9): (0.05～0.3):
(0.01～0.1).
2. the preparation method of a nickel cobalt aluminum ternary lithium ion anode material, it is characterised in that comprise the steps:
(1) method described in claim 1 is used to prepare hollow Hemicentrotus seu Strongylocentrotus shape nickel cobalt aluminum complex hydroxide presoma；
(2) by presoma and lithium salts ethanol mixed grinding post-drying；
(3) calcine under the atmosphere of oxygen, after cooling, obtain lithium nickel cobalt aluminum oxide ternary anode material.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described step
Suddenly nickel cobalt aluminum complex hydroxide presoma and lithium salts nLi:(nNi+nCo+nAl in molar ratio in (2)) ratio of=1.0-1.1 mixes.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described lithium
Nickel cobalt aluminum oxide ternary anode material chemical formula is Li (NixCoyAl1-x-y)O2, wherein 0.4≤x≤0.9,0.05≤y≤0.3.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described step
Suddenly first nickel salt and cobalt salt being mixed hydro-thermal 4～8h in (1), add aluminium salt hydro-thermal 8h-20h, hydrothermal temperature is 130～220 DEG C.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described step
Suddenly with the pH value of carbamide regulation reaction solution in (1), Ni, Co, Al tri-element mole total amount and the mol ratio of carbamide be
1:2。
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described step
Suddenly in (2), lithium salts is the one of lithium sulfate, lithium nitrate, lithium chloride, lithium acetate, lithium oxalate.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described step
Suddenly in (3), the atmosphere of calcining is oxygen, and the temperature of calcining is 500～850 DEG C, and the time of calcining is 4～10h.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described step
Suddenly the mixture of nickel cobalt aluminum complex hydroxide presoma and lithium salts is placed in tube furnace with the speed of 8～10 DEG C/min by (3)
Heating up, in the atmosphere of oxygen, oxidizing roasting obtains lithium nickel cobalt aluminum oxide ternary anode material.
The preparation method of nickel cobalt aluminum ternary lithium ion anode material the most according to claim 2, it is characterised in that: described
Nickel salt, cobalt salt and aluminium salt be respectively corresponding sulfate, nitrate, chlorate, acetate and oxalates one therein.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450216A (en) * | 2016-11-07 | 2017-02-22 | 珠海格力电器股份有限公司 | Modified nickel-cobalt-aluminum cathode material and preparation method thereof |
| CN106558695A (en) * | 2016-10-25 | 2017-04-05 | 荆门市格林美新材料有限公司 | A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof |
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| CN114933338A (en) * | 2022-07-04 | 2022-08-23 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-aluminum positive electrode material precursor and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106558695A (en) * | 2016-10-25 | 2017-04-05 | 荆门市格林美新材料有限公司 | A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof |
| CN106450216A (en) * | 2016-11-07 | 2017-02-22 | 珠海格力电器股份有限公司 | Modified nickel-cobalt-aluminum cathode material and preparation method thereof |
| CN107845789A (en) * | 2017-10-11 | 2018-03-27 | 苏州宇量电池有限公司 | A kind of synthetic method of cube structure high-performance lithium-rich manganese-based anode material |
| CN107845789B (en) * | 2017-10-11 | 2020-09-01 | 苏州宇量电池有限公司 | Method for synthesizing high-performance lithium-rich manganese-based cathode material with cubic structure |
| CN109473667A (en) * | 2017-10-23 | 2019-03-15 | 北京当升材料科技股份有限公司 | Lithium ion battery presoma, positive electrode and preparation method thereof |
| CN109473667B (en) * | 2017-10-23 | 2020-06-02 | 北京当升材料科技股份有限公司 | Precursor for lithium ion battery, positive electrode material and preparation method of precursor |
| JP2020087612A (en) * | 2018-11-20 | 2020-06-04 | 株式会社豊田自動織機 | Positive electrode material containing metal oxide having aluminum-containing coating formed on surface and aluminum-containing needle-like substance, and manufacturing method thereof |
| JP7135773B2 (en) | 2018-11-20 | 2022-09-13 | 株式会社豊田自動織機 | Cathode material containing a metal oxide with an aluminum-containing coating formed on the surface and an aluminum-containing needle-like substance, and a method for producing the same |
| CN109860540A (en) * | 2018-12-20 | 2019-06-07 | 天津巴莫科技股份有限公司 | A kind of high performance nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN110571066A (en) * | 2019-10-05 | 2019-12-13 | 浙江理工大学 | Preparation method of aluminum sulfide cobalt-graphene oxide composite flexible carbon nanofiber |
| CN114933338A (en) * | 2022-07-04 | 2022-08-23 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-aluminum positive electrode material precursor and preparation method thereof |
| CN114933338B (en) * | 2022-07-04 | 2024-03-01 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-aluminum positive electrode material precursor and preparation method thereof |
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